Microwave induced plasma atomic emission detector

The gas chromatograph may be interfaced with atomic spectroscopic instruments for specific element detection. This powerful combination is useful for speci-ation of different forms of toxic elements in the environment. For example, a helium microwave induced plasma atomic emission detector (AED) has been used to detect volatile methyl and ethyl derivatives of mercury in fish, separated by GC. Also, gas chromatographs are interfaced to inductively coupled plasma-mass spectrometers (ICP-MS) in which atomic isotopic species from the plasma are introduced into a mass spectrometer (see Section 20.10 for a description of mass spectrometry), for very sensitive simultaneous detection of species of several elements. 

As noted earlier, USNs have been employed for sample insertion into atomic spectrometers suoh as flame atomio absorption spectrometry (FAAS) [9,10], electrothermal atomic absorption speotrometry (ETAAS) [11], atomic fluorescence spectrometry (AFS) [12,13], induotively ooupled plasma-atomic emission spectrometry (ICP-AES) [14,15], inductively coupled plasma-mass spectrometry (ICP-MS) [16,17] and microwave induced plasma-atomic emission spectrometry (MIP-AES) [18,19]. Most of the applications of ultrasonic nebulization (USNn) involve plasma-based detectors, the high sensitivity, selectivity, precision, resolution and throughput have fostered their implementation in routine laboratories despite their high cost [4]. 

HPLC, coupled with element-specific detectors such as AAS, AFS, ICP-MS and microwave-induced plasma atomic emission spectrometry (MIP-AES). In general, methods for mercury speciation are classified according to the isolation/separation technique and the detection systems (Horvat 1996, Carro and Mejuto 2000). Most methods for isolation/separation are based on solvent extraction, differential reduction, difference calculation between total and ionic mercury, derivatization, or on paper- and thin-layer chromatography. 

Atomic absorption spectrometry (AAS) was established as the most popular gas chromatography (GC) detection technique for lead speciation analysis in the first years of speciation studies. The increase of the residence time of the species in the flame using a ceramic tube inside the flame and, later, the use of electrically heated tubes, made out of graphite or quartz where electrothermal atomization was achieved, provided lower detection limits but still not sufficiently low. Later, the boom of plasma detectors, mainly microwave induced plasma atomic emission (MIP-AES) and, above all, inductively coupled plasma atomic emission and mass spectrometry (ICP-AES and ICP-MS, respectively) allowed the sensitivity requirements for reliable organolead speciation analysis in environmental and biological samples (typically subfemtogram levels) to be achieved. These sensitivity requirements makes speciation analysis of organolead compounds by molecular detection techniques such as electrospray mass spectrometry (ES-MS) a very difficult task and, therefore, the number of applications in the literature is very limited. 

Several detectors are used for VOCs analysis by GC flame ionization detector (FID), photo ionization detector (PID), electron capture detector (BCD), electrolytic conductivity detector (ELCD), mass spectrometer detector (MSD or MS), and Fourier-transform infrared detector (FTIRD). For the in-depth reviews of the detectors, readers are directed to Refs. [52-54]. Examples of ICP-MS or microwave-induced plasma atomic emission spectrometry (atomic emission detector, AED) have been reported as detection technique after chromatographic separation [55,56]. Current trends and developments in GC analysis of VOCs have been recently reviewed by the group of Dewulf [16,57]. Mass spectrometer detectors allow low detection limits in single/selected ion monitoring (SIM) and a qualitative confirmation by full scan mode or by means of other ion selected as qualifier. 

Liu, Y. and Lopez-Avila (1993) On-line microwave-induced helium plasma atomic emission detector for capillary zone electrophoresis./. High Resol. Chromatogr., 16, 717-720. 

HPLC-QFAAS is also problematical. Most development of atomic plasma emission in HPLC detection has been with the ICP and to some extent the DCP, in contrast with the dominance of the microwave-induced plasmas as element-selective GC detectors. An integrated GC-MIP system has been introduced commercially. Significant polymer/additive analysis applications are not abundant for GC and SFC hyphenations. Wider adoption of plasma spectral chromatographic detection for trace analysis and elemental speciation will depend on the introduction of standardised commercial instrumentation to permit interlaboratory comparison of data and the development of standard methods of analysis which can be widely used. 

The atomic emission detector is a tunable, element-specific detector that uses microwave-induced helium plasma to generate temperatures high enough to break molecular bonds. The generated free atomic species undergo electron excitation to higher energy states, followed by relaxation and photon emission at characteristic frequencies... 

Microwave-induced plasma (MIP), direct-current plasma (DCP), and inductively coupled plasma (ICP) have also been successfully utilized. The abundance of emission lines offer the possibility of multielement detection. The high source temperature results in strong emissions and therefore low levels of detection. Atomic absorption (AA) and atomic fluorescence (AF) offer potentially greater selectivity because specific line sources are utilized. On the other hand, the resonance time in the flame is short, and the limit of detectability in atomic absorption is not as good as emission techniques. The linearity of the detector is narrower with atomic absorption than emission and fluorescence techniques. 

Online applications are by far the most important utilization of diode array spectrometry. High-performance liquid chromatography, supercritical fluid chromatography, capillary electrophoresis, and flow-injection techniques produce enhanced sensitivity and structure-related information due to coupling with diode-array-based detectors. Emission of the microwave-induced plasma generated in atomic emission detectors for capillary gas chromatography is also analyzed by means of UV-Vis diode array instruments. 

In 1989, Hewlett-Packard introduced a modernized and totally automated atomic emission detector (AED) connected with a GC equipped with a capillary column. At present, two names are used for the device GC-AED and (less frequently) GC-AES. The device utilizes a microwave-induced helium plasma for decomposition and excitation of analyzed compounds, and a photodiode array (PDA) for light emission measurement. The GC-AED may be used alone or in conjunction with GC-MS, and the situation allows for more effective use of both devices together than separately. 

In the atomic emission detector (AED), the effluent from the GC column is introduced into a microwave-induced plasma (MIP), an inductively coupled plasma (ICP), or a direct current plasma (DCP). The MIP has been most widely used and is available commercially. The MIP is used in conjunction with a diode array or charge-coupled-device atomic emission spectrometer as shown in Figure 27-12. The pl ma is sufficiently en-... 

Common gas chromatographic detectors that are not element- or metal-specific, atomic absorption and atomic emission detectors that are element-specific, and mass spectrometric detectors have all been used with the hydride systems. Flame atomic absorption and emission spectrometers do not have sufficiently low detection limits to be useful for trace element work. Atomic fluorescence [37] and molecular flame emission [38-40] were used by a few investigators only. The most frequently employed detectors are based on microwave-induced plasma emission, helium glow discharges, and quartz tube atomizers with atomic absorption spectrometers. A review of such systems as applied to the determination of arsenic, associated with an extensive bibliography, is available in the literature [36]. In addition, a continuous hydride generation system was coupled to a direct-current plasma emission spectrometer for the determination of arsenite, arsenate, and total arsenic in water and tuna fish samples [41]. 

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